Theoretical Modeling of Bioinorganic Copper Complexes

在这个项目中，我们通过计算探索了在SP3（双氧和-2:2-过氧铜配合物）、SP4 （CuA模型配合物）和SP5（零型模型配合物）下合成的铜基仿生配合物的基态和激发态性质。计算主要基于密度泛函理论（DFT）。将使用多体微扰理论（MBPT）或时变DFT技术计算激发态。我们的项目有两个目的：一方面，我们的目标是深入细致地了解电子结构和高度有趣的模型系统的相关功能。因此，我们特别感兴趣的是这些配合物的自旋结构，它们的结构和电子自由度在激发时的时间演变，以及相关化学反应的最重要步骤的热力学和动力学，如酪氨酸酶催化循环或电子转移反应。另一方面，我们希望协助研究单位的实验组对测量数据进行解释。因此，我们将计算光谱指纹，可以与UV/Vis，拉曼和EPR光谱进行比较，并协助解释x射线吸收数据。

Within this project we explore computationally the ground- and excited-state properties of copper-based biomimetic complexes synthesized in SP3 (bis--oxo and -2:2-peroxo dicopper complexes), SP4 (CuA model complexes) and SP5 (Type Zero model complexes). The calculations are mainly based on density functional theory (DFT). Excited electronic states will be calculated using either techniques of many-body perturbation theory (MBPT) or time-dependent DFT. The purpose of our project is two-fold: On the one hand, we aim at deep and detailed insight into the electronic structure and the related functionality of highly interesting model systems. Thereby we are in particular interested in the spin structure of these complexes, the time evolution of their structural and electronic degrees of freedom upon excitation, as well as the thermodynamics and kinetics of the most important steps of relevant chemical reactions such as the tyrosinase catalytic cycle or electron transfer reactions. On the other hand, we want to assist the experimental groups of the research unit in the interpretation of the measured data. Therefore we will calculate spectroscopic fingerprints that can be compared with the UV/Vis, Raman and EPR spectra and assist in the interpretation of X-ray absorption data.